Fluorinated cyclic alcohols



United States Patent 3,415,892 FLUORINATED CYCLIC ALCOHOLS Ogden R. Pierce, George A. Grindahl, and Anthony J.

Butler, Midland, Mich., assignors to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Original application Feb. 7, 1964, Ser. No. 343,201, now Patent No. 3,249,596, dated May 3, 1966. Divided and this application June 24, 1965, Ser. No.

5 Claims. (Cl. 260617) where R can be fluorine, hydrogen, or a perfiuoroalkyl radical, R and R" are lower alkyl radicals or hydrogen, and rt is an integer of 1 through 3.

These alcohols can be made by reacting with RI HJJOH in the presence of a free radical initiator such as ditertiary butyl peroxide at a temperature above the dissociation temperature of the free radical initiator, usually about 75 C. The maximum temperature is the point where the initiator dissociates too fast, about 150 C. The alcohol adds across the double bond of the cyclofluoroolefin, an alpha-hydrogen of the alcohol going to one olefinic carbon atom and the alcohol itself going to the other.

R can be fluorine, hydrogen, or any perfluoroalkyl radical such as trifluonomethyl, pentafluoroethyl, perfiuoroisobutyl, or perfiuorooctyl.

R and R" can be hydrogen or any lower alkyl radical such as methyl, ethyl, isobutyl, or hexyl.

The alcohols of this invention can be esterified with acrylic or methacrylic acid to form monomers from which the polymers of this invention can be made.

3,415,892 Patented Dec. 10, 1968 The esterified composition of this invention has the following formula:

where Q is either methyl or hydrogen.

These esters polymerize in the presence of free radical generators such as ditertiary butyl peroxide, through the opening up of the double bond on each ester molecule to form long chain polymers with pendent groups, each polymer unit, therefore, being The following examples are illustrative only and should not be construed limiting the invention, which is properly delineated in the appended claims.

Example 1 484 g. of perfluorocyclopentene, 150 g. of anhydrous methanol, and 10 g. of ditertiary butyl peroxide were placed in an evacuated, chilled stainless steel bomb. The bomb was placed on a rocker and heated overnight at C. the heat being controlled by an inside thermocouple.

The bomb was removed from the rocker, chilled, vented, and the contents fractionated.

266 g. of

were recovered, which is 78% of the theoretical yield. Example 2 A stainless steel bomb was evacuated, chilled, and charged with 316 g. of perfluorocyclopentene, g. of absolute ethanol, and 7 g. of ditertiary butyl peroxide. The bomb was heated at 120 C. overnight.

'Ihe bomb was chilled, vented, and the contents fractionated.

A sizea'ble yield of was recovered.

Example 3 When 15 g. each of the following fluorinated cycloolefins are reacted with 10 g. each of the following alcohols in the presence of 1 g. of ditertiary butyl peroxide, the following products are formed:

Olefin Alcohol Product CH3 CH3 CFzCFzCF=OF CHOH CFzOFgCHFOFOH CH CH flF13CFCF2CF=CF CaHrgCHzOII O6F13CFCF2CHFCFCHOH Ca ia r 1 r CH(CF) OF=CF CH CHzCHCH2OH CH(CF)gCFI-ICFOHOH L l I L... I

CH3 HCH2CH3 CFg(CF2)aOF=OF 021160112011 CMGFmGFI-ICFGHOH L L J CZH5 CF CF(CFH)3CF=CF CH OH CF oFwFPDaCFHCFCHgOH L. ...l L J Example 4 3 OFKCFmCFHSZFCHZOI-I When 15 g. each of the following fluorinated cycloolefins are reacted with 10 g. each of the following alcohols in the presence of 1 g. of ditertiary butyl peroxide, WEE FEJHOH the following products are formed: CH;

Olefin Product 5 OFflCFQMCFHSJFCIIHOI-I CF2(CF2)3CF=CF CF2(CF2)3CFHCFCH:OH OH;

OF2(CFz)aCF=CF 02115011 crncrmcrncrcnon References Cited 5 UNITED STATES PATENTS 2,601,075 6/1952 Wicklatz et al. 260-617 X That which is claimed 1s: 2,871,255 1/ 1959 Molotsky et a1. 260617 X 1. A composition of the formula 3,283,012 11/1966 Day 260-617 f OTHER REFERENCES CRF(ORF)OFHF(I3OH Coffman ct al.: J. Am. Chem. Soc., vol. 71, p. 494

Where R is selected from the group consisting of fluorine,

hydrogen, and perfiuoroalkyl radicals, R and R are 4 4670'1,

each selected from the group consisting of hydrogen and lower alkyl radicals, and n is an integer of 1 through 3.

LEON ZITVER, Primary Examiner.

T. G. DILLAHUNTY, Assistant Examiner.

Andreades et al.: J. Am. Chem. 500., vol. 83, pp. 

1. A COMPOSITION OF THE FORMULA 